The present invention relates to new fluoromonomers having the generic structure: CF2xe2x95x90CF(OCH2CH2)nOR where n is an integer and R is a functional group and methods for producing same. The present invention also relates to new fluoropolymers prepared from any one or combination of the new fluoromonomers and having the generic structure: xe2x80x94[xe2x80x94CF2CF{(OCH2CH2)nOR}xe2x80x94]mxe2x80x94 where n is an integer, m is an integer and R are any one or combination of functional groups. The method also relates to new copolymers or terpolymers prepared from the new fluoromonomers alone, the new fluoromonomers and existing fluoromonomers or the new fluoromonomers and existing hydrocarbon monomers.
Fluoromonomers
1-alkoxy/aryloxy-1,2,2-trifluoroethenes or 1-(substituted)fluoro/perfluoroalkoxy-1,2,2-trifluoroethenes(trifluorovinyl ethers or TFVEs) have been previously synthesized by two principal synthetic routes that do not involve the use of elemental halogens or hydrogen fluoride.
For example, U.S. Pat. No. 2,917,548 to Dixon [1] discloses the preparation and polymerization of 1-methoxy-1,2,2-trifluoroethene which was prepared by the reaction of sodium methoxide with tetrafluoroethylene. This reaction was expanded by Okuhara, et al. Bull. Chem. Soc. Jap. 1962, 35, 532-535 [2] to include ethoxide, isopropoxide and tert-butoxide substituted TFVEs. 1-ethoxy-1,2,2-trifluoroethene was polymerized with xe2x80x9ccommon free radical initiatorsxe2x80x9d. This method required high pressure reaction equipment to achieve high tetrafluoroethylene pressures and long reaction times (and in one instance an explosion was reported) [2].
U.S. Pat. No. 3,277,068 to Wall et al. [3] discloses the preparation of 1-phenoxy-1,2,2-trifluoroethenes, and polymers derived therefrom. The monomer was prepared by the reaction of an alkali metal phenoxide with tetrafluoroethylene. Tetrafluoroethylene pressures greater 200 PSI were required. No phase transfer catalyst was used.
U.S. Pat. No. 5,162,468 to Babb et al. [4] and U.S. Pat. No. 5,198,513 to Clement et al. [5] disclose the preparation and polymerization of trifluorovinyl compounds, CF2xe2x95x90CFxe2x80x94Oxe2x80x94Rxe2x80x94(Oxe2x80x94CFxe2x95x90CF2)m, where R represents an unsubstituted or inertly substituted hydrocarbyl group and m is an integer of from 1 to 3. These compounds were prepared by reaction of an appropriate salt with 1,2-dihalo-1,1,2,2-tetrafluoroethane to form intermediates, Zxe2x80x94CF2CF2xe2x80x94Oxe2x80x94Rxe2x80x94(Oxe2x80x94CF2CF2xe2x80x94Z)m, where each Z is independently iodine or bromine. Elimination of the halogen atoms represented by Z formed the trifluorovinyl compounds.
U.S. Pat. No. 3,114,778 to Fritz et al. [6], U.S. Pat. No. 3,180,895 to Harris et al. [7], and U.S. Pat. No. 3,250,808 to Moore et al. [8] disclose a method to prepare 1-fluoro/perfluoroalkoxy-1,2,2-trifluoroethenes, and polymers derived therefrom. These monomers where prepared by pyrolysis of 2-fluoro/perfluoroalkoxy-2,3,3,3-tetrafluoropropionic acid intermediates or derivatives thereof. U.S. Pat. No. 5,391,796 to Farnham [9] discloses a method to prepare 1-(substituted)fluoro/perfluoroalkoxy-1,2,2-trifluoroethenes, and polymers derived therefrom. These monomers were prepared by pyrolysis of compounds represented by R1xe2x80x94Oxe2x80x94(C2F4)CO2SiR23, where R1 represents an unsubstituted or inertly substituted hydrocarbyl or fluorocarbyl group and R2 is independently hydrocarbyl, substituted hydrocarbyl or an oxysilyl group.
Pellerite J. Fluorine Chem. 1990, 49, 43-46 [10] reported the synthesis of 1-alkoxy-1,2,2-trifluoreoethenes by pyrolysis of 2-alkoxy-2,3,3,3-tetrafluoropropionate salts. The pyrolysis resulted in unanticipated chemistry with negligible to low yields of 1,2,2-trifluoroethenes depending on the alkoxy substituent and propionate counterion.
U.S. Pat. No. 4,337,221 [11] and U.S. Pat. No. 4,515,989 to Ezzell et al. [12] disclose the preparation 1-(substituted)fluoro/perfluoroalkoxy-1,2,2-trifluoroethenes and polymers derived therefrom. The former were prepared from 2-fluoro/perfluoroalkoxy-3-chloro-2,3,3-trifluoropropionyl fluoride intermediates. The intermediates reacted with sodium carbonate at temperatures between ambient and 80xc2x0 C. to form the monomers in very high yields.
Fluoropolymers
Fluorochemicals are hydrophobic, oleophobic and have extremely low surface energies, making them useful blooming agents in processing applications [13]. Fluoropolymers are chemically inert having unique properties of thermal stability and biological acceptability. Consequently, they have been used in numerous applications, from chemical erosion resistant devices to coatings and linings in chemical storage tanks to vascular grafts [13]. Commercial fluoropolymers have been used as coatings and include, for example: (1) a block terpolymer of 65% vinylidene fluoride, 25% tetrafluoroethylene and 10% vinyl ester (e.g. vinyl butyrate) which can be cured by UV-irradiation; (2) tetrafluoroethylene-hydroxyalkyl vinyl ether copolymer which is used in acrylic sheets; (3) fluoroolefin-vinyl ether copolymers, Lumiflon(copyright) comprises alternating sequences of fluoroolefin and several specific vinyl monomer units.
Fluoropolymers, such as poly(tetrafluoroethylene) or poly(tetrafluoroethylene-co-hexafluoropropylene), are difficult to process, insoluble in common organic solvents and chemically inert, requiring highly reactive species for surface modification [14]. Perfluorinated ether groups on trifluorovinyl ethers (TFVEs) have been shown to improve the processability of the resulting polymer [15]. Incorporating a hydrocarbon ether group into the fluoromonomer will likely further improve the processability of the resulting polymers; however no one has yet synthesized (or polymerized) the hydrocarbon TFVEs described herein. The hydrocarbon ether group is anticipated to improve the solubility of the resulting poly(TFVE)s in common organic solvents, thereby further expanding the range of applications.
It is an object of the present invention to provide new fluoromonomers, a method for their production and fluoropolymers produced from the fluoromonomers.
The present invention provides new fluoromonomers having the generic structure: CF2xe2x95x90CF(OCH2CH2)nOR where n is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group. A new method of synthesizing the fluoromonomers is provided. The present invention also relates to new fluoropolymers prepared from any one or combination of the new fluoromonomers and having the generic structure: xe2x80x94[xe2x80x94CF2CF{(OCH2CH2)nOR}xe2x80x94]mxe2x80x94 where n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group. The method also relates to new copolymers or terpolymers prepared from the new fluoromonomers alone, the new fluoromonomers and existing fluoromonomers or the new fluoromonomers and existing hydrocarbon monomers.
The present invention provides a fluoromonomer of the following general formula (I), comprising;
CF2xe2x95x90CF(OCH2CH2)nORxe2x80x83xe2x80x83(I)
wherein n is an integer greater than or equal to 1 and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group.
The invention also provides a process for synthesis of a fluoromonomer having the following general formula (I),
CF2xe2x95x90CF(OCH2CH2)nORxe2x80x83xe2x80x83(I)
wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, comprising the steps of:
providing an effective alkali metal alkoxide;
mixing tetrafluoroethylene with said alkali metal alkoxide in the presence of an effective phase transfer catalyst at an effective temperature to form a mixture, the phase transfer catalyst being selected from the group consisting of crown ethers and tetraalkylammonium salts; and isolating the fluoromonomer from the mixture.
The invention also provides a fluoropolymer of the following general formula (II), comprising
xe2x80x94[CF2CF{(OCH2CH2)nOR}]mxe2x80x94xe2x80x83xe2x80x83(II)
wherein n is an integer, m is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group.
The invention provides copolymers comprising a first fluoromonomer of the general formula CF2xe2x95x90CF(OCH2CH2)nOR, wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, and a second monomer of the general formula CF2CXY wherein X and Y are selected from the group consisting of hydrogen, halogen, hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof. Alternatively, the second monomer may be a second fluoromonomer of the general formula CFXCYZ, wherein n is an integer, wherein R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein X, Y and Z are selected from the group consisting of hydrogen, halogens, unsubstituted hydrocarbyl and inertly substituted hydrocarbyl groups and any combination thereof. Alternatively, the second monomer may have a generic formula CXYCAB wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.
The present invention provides a fluoromonomer of the following general formula CGJxe2x95x90CL(OCH2OCH2)nOR wherein n is an integer, and wherein R represents an unsubstituted or inertly substituted hydrocarbyl group. G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine.
The present invention provides a fluoropolymer of the following general formula, comprising xe2x80x94[CGJCL{(OCH2CH2)nOR}]mxe2x80x94, wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine.
Copolymers are provided comprising a fluoromonomer of the general formula CGJxe2x95x90CL(OCH2CH2)nOR, wherein G and J are selected from the group consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L is selected from the group consisting of chlorine, fluorine and hydrogen, and wherein at least one of G, J and L is fluorine. The copolymers may be produced using a second fluoromonomer of the general formula CF2CXY, wherein n is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group, and wherein X and Y are selected from the group consisting of hydrogen, halogens, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof. Alternatively, the second monomer may be of the general formula CFXCYZ, wherein X, Y and Z are selected from the group consisting of hydrogen, halogens, hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof. Or, alternatively the second monomer may have a generic formula CXYCAB, wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof.
The invention also provides a terpolymer comprising a first fluoromonomer of the following general formula
CF2xe2x95x90CF(OCH2CH2)nOR
wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group, and a second fluoromonomer of the following general formula
CF2xe2x95x90CF(OCH2CH2)nORxe2x80x2
wherein n is an integer greater than or equal to 1 and Rxe2x80x2 represents an unsubstituted or inertly substituted hydrocarbyl group, wherein R and Rxe2x80x2 are different. The terpolymer includes a third fluoromonomer which may have the general formula 1) CF2CXY, wherein X and Y are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof; or 2) a fluoromonomer of the general formula CFXCYZ, wherein X, Y and Z are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl and inertly substituted hydrocarbyl groups and any combination thereof; or 3) a monomer having a generic formula CXYCAB, wherein X, Y, A, B are selected from the group consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl groups and any combination thereof; or 4) a fluoromonomer of the following general formula
xe2x80x83CF2xe2x95x90CF(OCH2CH2)nORxe2x80x3
wherein n is an integer greater than or equal to 1 and Rxe2x80x3 represents an unsubstituted or inertly substituted hydrocarbyl group, wherein R, Rxe2x80x2 and Rxe2x80x3 are different from each other.
The present invention provides a graft copolymer comprising a polymer graft and a polymer backbone, the backbone comprising a polymer selected from the group consisting of polystyrene, polyurethane, polyester, polyether, polyethylene, polypropylene, poly(carbonate), poly(anhydride), poly(vinyl chloride), poly(acrylonitrile), poly(xcex1-hydroxyesters), poly(tetrafluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino acid), poly(arylate), poly(acrylate), poly(acetate) and any combination thereof; and the polymer graft comprising a fluoropolymer of the following general formula xe2x80x94[CF2CF{(OCH2CH2)nOR}]mxe2x80x94 wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group.
The present invention provides a fluoropolymer blend comprising a fluoromonomer of the following general formula CF2xe2x95x90CF(OCH2CH2)nOR wherein n is an integer greater than or equal to 1 and R represents an unsubstituted or inertly substituted hydrocarbyl group; and a polymer selected from the group consisting of polystyrene, polyurethane, polyester, polyether, polyethylene, polypropylene, poly(carbonate), poly(anhydride), poly(vinyl chloride), poly(acrylonitrile), poly(xcex1-hydroxyesters), poly(tetrafluoroethylene), poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino acid), poly(acrylate), poly(acetate) and any combination thereof.
The fluoropolymer blends may also be produced using the fluoropolymer of the following general formula xe2x80x94[CF2CF{(OCH2CH2)nOR}]mxe2x80x94 wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group and the polymers listed above.
In another aspect of the invention there is provided biologically useful materials exhibiting low protein absorption comprising fluoropolymers blended with biologically acceptable polymer, the fluoropolymers being selected from the group consisting of xe2x80x94[CF2CF{(OCH2CH2)nOR}]mxe2x80x94, wherein n is an integer, m is an integer and R represents an unsubstituted or inertly substituted hydrocarbyl group.